2569-58-6Relevant articles and documents
Azobenzene-Appended Bis-Cyclometalated Iridium(III) Bipyridyl Complexes
Telleria, Ainara,Pérez-Miqueo, Jorge,Altube, Ainhoa,García-Lecina, Eva,De Cózar, Abel,Freixa, Zoraida
, p. 5513 - 5529 (2015)
A new synthetic route toward photochromic azobenzene-appended bipyridyl ligands has been developed, and 20 new cationic iridium(III) bis-cyclometalated complexes containing up to four azobenzene fragments on their structure have been synthesized and characterized electronically and spectroscopically. These compounds incorporate photochromic azobenzene units in their neutral pyridyl ligands 1-5, and in four of them azobenzenes have been also introduced a posteriori on their phenylpyridyl ligands by palladium-catalyzed cross-coupling. UV-vis-monitored light-triggered trans-to-cis isomerization of the azobenzene-appended ligands revealed a strong inhibition of this process upon coordination to the d6-metal ion. TD-DTF calculations revealed that this inhibition could be a consequence of a metal to ligand charge transfer relaxation process.
Photosensitive and Photoswitchable TRPA1 Agonists Optically Control Pain through Channel Desensitization
Luo, Jiajie,Qi, Hang,Qiao, Zhen,Tang, Xiaowen,Tang, Yi-Quan,Wang, KeWei,Wei, Ningning,Yin, Zhengji,Zhang, Yanru,Zhou, Qiqi,Zhu, Wei
supporting information, p. 16282 - 16292 (2021/11/12)
Transient receptor potential ankyrin 1 (TRPA1) channel, as a nonselective ligand-gated cation channel robustly in dorsal root ganglion sensory neurons, is implicated in sensing noxious stimuli and nociceptive signaling. However, small-molecule tools targeting TRPA1 lack temporal and spatial resolution, limiting their use for validation of TRPA1 as a therapeutic target for pain. In our previous work, we found that 4,4′-(diazene-1,2-diyl)dianiline (AB1) is a photoswitchable TRPA1 agonist, but the poor water solubility and activity hinder its further development. Here, we report a series of specific and potent azobenzene-derived photoswitchable TRPA1 agonists (series 1 and 2) that enable optical control of the TRPA1 channel. Two representative compounds 1g and 2c can alleviate capsaicin-induced pain in the cheek model of mice through channel desensitization but not in TRPA1 knockout mice. Taken together, our findings demonstrate that photoswitchable TRPA1 agonists can be used as pharmacological tools for study of pain signaling.
Thermal spin crossover behaviour of two-dimensional hofmann-type coordination polymers incorporating photoactive ligands
Ragon, Florence,Yaksi, Korcan,Sciortino, Natasha F.,Chastanet, Guillaume,Ltard, Jean-Francois,D'Alessandro, Deanna M.,Kepert, Cameron J.,Neville, Suzanne M.
, p. 1563 - 1573 (2015/01/09)
Two spin crossover (SCO)-active 2D Hofmann-type framework materials, [Fe(3-PAP)2Pd(CN)4] (A) and [Fe(4-PAP)2 Pd(CN)4] (B) containing the photoactive azo-benzene-type ligands 3-phenylazo-pyridine (3-PAP) and 4-phenylazopyridine (4-PAP) were prepared. These materials form non-porous Hofmann-type structures whereby 2D [FeIIPd(CN)4] grids are separated by 3- or 4-PAP ligands. The iron(II) sites of both materials (A and B) undergo abrupt and hysteretic spin transitions with characteristic transition temperatures T1/2↓,↑: 178, 190K (ΔT: 12K) and T1/2↓,↑: 233, 250K (ΔT: 17 K), respectively. Photo-magnetic characterisations reveal light-induced excited spin state trapping (LIESST) activity in both A and B with characteristic T(LIESST) values of 45 and 40 K. Although both free ligands show trans- to-cis isomerisation in solution under UV-irradiation, as evidenced via absorption spectroscopy, such photo-activity was not observed in the ligands or complexes A and B in the solid state. Structural analysis of a further non-SCO active isomer to B, [Fe(4-PAP)2 Pd(CN)4]·1/2(4-PAP) (B·(4-PAP)), which contains free ligand in the pore space is reported.
